Polymers permeate every aspect of today's society. Moreover, advances in our society are keenly tied to advances in new materials, particularly polymers. Unfortunately, however, we are limited in the types of polymers that can be prepared. For example, polymers containing a wide variety of desirable functional groups can not be prepared, or if they can be prepared, it is only with great difficulty. Thus, using presently known techniques it is generally difficult to modify polymers. For example, it is typically difficult to modify the surfaces of polymers to attach dyes, UV stabilizers, or molecules that impart conducting properties, magnetic properties, nonlinear optical properties, etc.
Furthermore, insoluble polymers, such as cross-linked polystyrene resins and functionalized polystyrene resins, are highly desirable reagents in organic synthesis. For example, insoluble polymers are important reagents in organic synthesis as protecting groups and in asymmetric syntheses as chiral auxiliaries. They are also important reagents in solid-phase synthesis, and as supports for chromatography and catalysis.
Methods for chemically modifying polymers, i.e., functionalizing, polymers, such as cross-linked polystyrene resins, typically involve: (1) lithiation of p-bromopolystyrene; (2) lithiation of polystyrene; and (3) nucleophilic substitution on chloromethylated polystyrene. These transformations of insoluble polymers normally occur with a soluble reagent interacting in intimate fashion with an insoluble polymer. This occurs, for example, in the preparation of lithium and potassium derivatives of chloromethylated polystyrene. Furthermore, insoluble Grignard reagents have been prepared in THF from the addition of a soluble magnesium anthracene to lightly cross-linked polymers containing chloromethyl groups and alkyl/aryl bromides. These reagents, however, have limited applicability.
The use of functionalized polymers in organic chemistry, particularly those containing metal atoms, has been slowed by the insoluble form in which most metals are typically found. Thus, there are relatively few effective techniques available to prepare functionalized polymers, particularly containing metal atoms.
An object of this invention is to generate novel functionalized polymers, both soluble and insoluble, that may not be available using standard polymerization techniques. Furthermore, an object of this invention is to develop a method for modifying the surfaces of soluble and insoluble polymers to attach dyes, UV stabilizers, drug systems, biologically active substrates, molecules that impart conducting properties, magnetic properties, nonlinear optical properties, adhesive properties, thermal stability, or increased strength. Another object of this invention is to produce a wide variety of calcium-substituted polymeric reagents that can be used to produce new organic compounds, new functionalized polymers, and new, more direct methods of synthesis. Yet another object of this invention is to produce a wide variety of calcium-substituted polymeric reagents that can be used to produce novel polymers, which upon cleavage can be used to synthesize novel monomers and organic products.